Two series of chiral bulky vinyl monomers, 2-(4′-hexyloxyphenyl)-5-(4′-alkoxycarbonylphenyl)styrene and 2-(4′-alkoxycarbonylphenyl)-5-(4′-hexyloxyphenyl)styrene (abbreviated as S-(+)-HexMm/R-(−)-HexM0 and S-(+)-MmHex/R-(−)-M0Hex (m = 0, 1, 2, 3), respectively), were designed and synthesized. The former differed the latter only by the relative location of vinyl group, i.e., orientation against or toward the stereocenter. Except for S-(+)-HexM1 and S-(+)-HexM3, all the monomers readily underwent radical polymerization to yield the polymers displaying optical rotations and Cotton effects in the UV−vis absorption region of side groups distinct to the corresponding model compounds and mononmers, implying the formation of main chain chirality, most probable helicity. The influences of the configuration, the distance to p-terphenyl, and the position relative to vinyl group of stereocenter on the chiroptical properties of the resultant polymers were systematically studied. It was found that inverting the absolute...